Fracture behaviours of in situ silica nanoparticle-filled epoxy at different temperatures

Fracture behaviours of nanosilica filled bisphenol-F epoxy resin were systematically investigated at ambient and higher temperatures (23 °C and 80 °C). Formed by a special sol-gel technique, the silica nanoparticles dispersed almost homogenously in the epoxy resin up to 15 vol.%. Stiffness, strength and toughness of epoxy are improved simultaneously. Moreover, enhancement on fracture toughness was much remarkable than that of stiffness. The fracture surfaces taken from different test conditions were observed for exploring the fracture mechanisms. A strong particle-matrix adhesion was found by fractography analysis. The radius of the local plastic deformation zone calculated by Irwin model was relative to the increment in fracture energy at both test temperatures. This result suggested that the local plastic deformation likely played a key role in toughening of epoxy.     

Comparison of the Degradation Mechanisms of Zinc-Coated Steel, Cold-Rolled Steel, and Aluminium/Epoxy Bonded Joints

The durability properties of bonded lap shear joints made from an epoxy/dicyandiamide adhesive and zinc, zinc-coated steel, two different aluminium alloys or cold-rolled steel metal coupons have been investigated. The influence of the dicyandiamide content of the adhesive on the durability properties-has been assessed by salt spray testing or by storing the joints in water at 70°C or 90°C for periods of time up to five weeks. The degradation products formed during ageing of the epoxy adhesive in water have been investigated using high performance liquid chromatography (HPLC) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFT). The degradation mechanisms of aluminium/epoxy bonded joints have been thoroughly studied using X-ray photoelectron spectroscopy.

The performances of the bonded joints under a pure corrosive environment have been found to be little influenced by the quantity of dicyandiamide in the adhesive. When the bonded joints were aged in hot water, the stability of the interface toward an excess of dicyandiamide directly followed the sensitivity of the oxide layer at high pH values. Optimal durability properties without peel strength losses of the adhesive were aehieved both with zinc and aluminium-coated substrates by reducing the quantity of dicyandiamide in the epoxy adhesive by 20% (the initial dicyandiamide content in the commercial adhesive being ca. 9%, with respect to the epoxy resin).     

Mechanical properties,water absorption and adhesive properties of diepoxy aliphatic diluent-modified DGEBA/Cycloaliphatic amine networks on 316 L stainless steel

In this study, the mechanical behaviors, adhesive properties and water absorption of networks based on diglycidyl ether of bisphenol A (DGEBA) modified with diepoxy aliphatic diluent (1,4-butanediol diglycidyl ether, DGEBD) cured with cycloaliphatic amine were studied. The mechanical behaviors and adhesive properties were evaluated by compression testing and single lap-shear using 316 L stainless steel as the adherend, respectively. Water absorption was evaluated by water immersion at 37±0.2 °C. The fracture mechanisms of the networks were determined by optical microscopy. Decreases in the glass transition temperature (T_g) and the yield stress (σ) were noted with increased additive concentrations. The best mechanical performance, accompanied by slight increased adhesive strength, was obtained with 30 phr of additive. The DGEBA/4MPip network modified with 30 phr of diluent shows the best compressive behavior, adhesive strength, and lower water absorption. This behavior may relate to the lower crosslinking density resulting from the reaction mechanism, of stepwise and addition polymerization. Greater participation of cohesive fracture mechanisms was observed in the epoxy networks modified with 30 phr of additive.     

Effect of carbonization rate on the properties of a PAN/phenolic-based carbon/carbon composite

The effect of carbonization rate in a wide range (1, 100 and 1000 °C/min) on the properties of a PAN/phenolic-based carbon/carbon (C/C) composite was studied. The results indicated that the composite processed at a higher carbonization rate had a higher porosity level, more large pores and a more graphitic structure than that processed at a lower carbonization rate. After second graphitization the bending properties of composites carbonized at 1 °C/min and 1000 °C/min were comparable. The composite carbonized at 1000 °C/min had the highest fracture energy. The composite carbonized at 100 °C/min showed the worst mechanical performance among three. The large increase in carbonization rate can be beneficial to the industry from an economic point of view.     

The influence of storage and drying methods for Scots pine raw material on mechanical pellet properties and production parameters

Converting solid biomass into pellets through densification greatly improves logistical handling and combustion processes. Raw material properties can affect pellet quality. This study investigated how storage and drying methods for wood (Pinus sylvestris L.) used as a raw material for pellet production influenced pellet durability, bulk density and energy consumption. The pelletization experiments were performed using a Sprout Matador M30 press (nominal production capacity 3.5 tonnes/h). Results showed that pelletization of 11 months stored wood compared to fresh material and high drying temperature (450 °C) compared to 75 °C resulted in higher energy consumption, probably due to increased friction in the matrix caused by the loss of extractives. However, the pellets produced were of higher density than those made from fresh material dried at a low temperature. The latter had the highest durability. Increased energy consumption showed no correlation with pellet durability.     

Toughening mechanisms of rubber modified thin film epoxy resins

An epoxy terminated polybutadiene (ETPB) was synthesized and utilized to enhance the toughening of an epoxy system, in both bulk and coating states. In the first step, the fracture energy of the modified samples was determined using a single edge notched type specimen in a three point bending (SEN3PB) geometry. The effective toughening mechanisms of bulk epoxy specimens were examined using scanning electron microscopy (SEM). The results showed that plastic void growth, cavitation and shear yielding mechanisms were the main toughening mechanisms of the bulk epoxy systems. In the next step, mechanical properties (i.e. impact resistance, flexibility, cupping resistance and hardness) and adhesion of the thin film specimens were evaluated in accordance to the amount of synthesized ETPB. The results showed that the mechanical properties of the ETPB modified epoxy resins considerably improved. In all cases, it was found that the improvement of the mechanical properties reached a maximum at 7.5 wt.% and then began to decrease with further increase in ETPB content. The effective toughening mechanisms in the modified thin films were also examined using SEM and compared to the bulk types. In contrast to the bulk types, the results showed that crack arresting and shear yielding were active mechanisms in thin films. The contribution of these mechanisms led to the improvement of adhesion and mechanical properties by energy dissipation.     

Influence of copolymerisation on fracture behaviour of aliphatic polyketones

High strain rate tensile impact properties of aliphatic polyketone terpolymers were investigated and related to the polymer chain structure. Aliphatic polyketones were used as a model system, by changing the termonomer content and type. Aliphatic polyketone is a perfectly alternating copolymer and the structure was changed with the addition of a few mol% of termonomer: propylene, hexylene and dodecene. Studied were the thermal properties with DSC and DMTA, tensile behaviour, notched tensile impact behaviour, notched Izod properties and the temperature development during deformation. The perfectly alternating copolymer had a melting point of 257 °C, a T_g at 15 °C, a high crystallinity (48%), a high yield stress (77 MPa) and yield strain (31%) but a relatively low fracture strain (85%) and an impact strength (notched Izod) of 13 kJ/m². Increasing the propylene content to 6%, lowered the melting temperature to 224 °C, without changing the T_g. The modulus and yield stress were lowered but the impact strength improved. Increasing the length of the termonomer while keeping the T_m at 224 °C lowered the T_g, the modulus, the yield stress but strongly improved the impact resistance. The longer termonomers, with a lower yield stress, reduced the necking behaviour. The temperature increase in front of the notch was about 85 °C. By adding termonomers to aliphatic ketones, the notched impact behaviour improved significantly at the cost of modulus and yield stress.     

The influence of porosity and morphology of hydrated oxide films on epoxy-aluminium bond durability

Clad aluminium alloy was pretreated by immersion in boiling water for times ranging between 30 s and 4 h. The chemical and physical properties of the films produced in the 100°C water were characterized by techniques including X-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectroscopy (RBS), scanning electron microscopy (SEM), and secondary ion mass spectrometry (SIMS). The durability of the bonds formed between the boiling water films and a rubber-toughened epoxy adhesive was assessed in terms of the film properties and fracture analysis of failed wedge specimens. In the early pretreatment stage, bond durability was limited by the fracture of the porous oxide film at the film-metal interface. For immersion times greater than 4 min, a decrease in film porosity and bond durability was observed.     

Durability of Aluminium Adhesive Joints Bonded with a Homopolymerised Epoxy Resin

The durability of epoxy-aluminium joints that use a homopolymerised epoxy resin was studied, and the effects of relative humidity, temperature, and salt concentration were analysed. The adhesive properties were measured by lap-shear tests, and the water uptake of the epoxy resin was determined by gravimetric measurements. Ageing and degradation effects on the epoxy resin and on the aluminium substrates were also analysed.

The homopolymerised epoxy resin absorbs little water (1.5 wt%) because of its nonpolar network structure. The water uptake is enhanced by increasing relative humidity and temperature; however, the joint strength remains constant because of epoxy plasticization. A saline environment is damaging to the adhesive joints, because of metal corrosion, but was not significantly harmful to the epoxy resin, because of a lower diffusion coefficient of salt water. The T_g decrease of the epoxy adhesive due to water absorption depends only on the amount of absorbed water and is independent of the hydrothermal ageing conditions.     

Anomalous but useful behavior of epoxy adhesive system

Freeze storage of adhesives has been an industry-wide practice for a long time. However, when the technique was applied to an epoxy adhesive, anomalous, but very useful results were obtained. Among other observations, the study showed that freeze storage changes the final properties of the epoxy. The epoxy was applied as an adhesive in the sealing of a component. Among adhesive candidates that were evaluated, the epoxy EA9396 was preferentially selected because it is amenable to room temperature cure and consequently it exhibits less stress and fracture upon cure. The formulation was frozen at −43 °C for different periods of time. A cure schedule consisting of 16 h at room temperature followed by two hours at 65 °C imparted shore D hardness of 80, shear strength of about 1800 psi and an extent of cure of 82% to the adhesive regardless of the length of the freezing time. Rheometry analysis of the thawed frozen formulation showed an anomalous trend whereby the pot life increased immensely in direct proportion to the duration of the freezing time. In this study pot life implies the working life after the frozen formulation is thawed. A pot life of 85 min was observed for samples cold-stored for three weeks. This method would offer advantages in applications requiring long pot and cold storage lives. This paper provides an insight into this phenomenon.     

Organically modified layered-silicates facilitate the formation of interconnected structure in the reaction-induced phase separation of epoxy/thermoplastic hybrid nanocomposite

We incorporated organic modified layered silicates (OLS) into the mixture of epoxy and poly(ether imide) (PEI) to obtain a ternary hybrid nanocomposite and investigated its reaction-induced phase separation behavior. We found that OLS had dramatic impact to the phase separation process and the final phase morphology. The onset of phase separation and the gelation or vitrification time were greatly brought forward and the periodic distance of phase-separated structure was reduced when OLS was incorporated. Phase separation of the unfilled specimens was greatly suppressed at temperatures higher than 190 °C, and no etch hole of PEI-rich phase could be observed in the SEM images. An interconnected, or bicontinuous morphology could only be observed at cure temperatures lower than 140 °C. On the contrary, the OLS-filled hybrid nanocomposites carried out obvious phase separation at cure temperatures ranging from 120 to 220 °C. Even at cure temperatures higher than 190 °C, the hybrid nanocomposites had an interconnected phase-separated microstructure. These phenomena were related to the preferential wettability, chemical reaction of OLS with epoxy oligomer and the enhanced viscosity of the mixture.     

Solid particle impact erosion of alumina-based refractories at elevated temperatures

Solid particle erosion tests have been conducted on three different alumina-based refractories at elevated temperatures up to 1400 °C, using sharp SiC particles between 325 and 830 μm in diameter. The impact speed is 50 m/s and the impact angle is varied between 30° and 90°. The objective of this study is to ascertain the effects of temperature and impact angle on the erosion resistance of alumina refractories. The experimental results reveal that the alumina-based refractories, in general, exhibit increasing erosion resistance with increasing temperature and decreasing impact angle, with the minimum erosion rate at 1200 °C and 30° impact angle. Chrome corundum refractory brick is the most resistant to vertical erosion, due to its highest alumina content, and associated hardness and density, as well as strongly bonded aggregate and binder phase. The primary material removal mechanisms are fracture and chipping of binder phase and aggregate, as well as aggregate pull-out.     

Characterization of high performance composite coating for the northern pipeline application

High performance composite coating (HPCC) provides a potential, excellent coating alternative for integrity maintenance of pipelines in the northern area. In this work, the physical, chemical and mechanical properties of HPCC were investigated to determine the microstructure, water permeability, cathodic disbondment resistance, electrochemical impedance, adhesion and impact resistance of the coating. It is shown that the addition of polyethylene layer significantly improves the compactness of the coating and enhances its resistance to water and chemical penetration, resulting in a small water vapor transmission rate and permeance. There is a quite small cathodic disbondment of HPCC under the standard test. The impedance characteristic measured on HPCC-coated steel shows a capillary behavior, indicating an effective protection over the underlying steel from corrosion. The adhesion of HPCC to the substrate ranks top one according to both ASTM and CSA standards. The impact energy of HPCC is 9.7 J at 22 °C, and about 10.2 J around 0 °C.     

The preparation and performance of short carbon fiber reinforced adhesive for bonding carbon/carbon composites

A short carbon fiber reinforced adhesive for bonding carbon/carbon composites was developed. We found that when the thickness of the bonding layer was 80 μm, the concentration of short carbon fiber was 0.2 wt.%, and the heat-treatment temperature was 1000 °C, the adhesive could operate below 1700 °C and endure 20 times of thermal shock circles at 1500 °C. Finite element and micrograph analysis indicated that the bonding strength was larger than the interlaminar shear strength of carbon/carbon substrate, so that the fracture did not occur in the bonding layer but the carbon/carbon substrate. Weibull distribution analysis results showed that the Weibull modulus was 21.56 and the bonding strength was 11.43 MPa. We investigated that short carbon fiber could advance the tensile strength and thermal shock resistance of the adhesive, release residual stress and inhibit extension of micro-crack in the bonding layer.     

Polysulfone ionomers for proton-conducting fuel cell membranes: 2. Sulfophenylated polysulfones and polyphenylsulfones

Polysulfones and polyphenylsulfones having pendant phenyl groups with sulfonic acid units have been prepared by lithiation of the respective polymer, followed by reaction with 2-sulfobenzoic acid cyclic anhydride. The resulting ionomers were cast into membranes and properties such as thermal stability, ion-exchange capacity, water sorption and proton conductivity were evaluated. These membranes proved to have a high thermal stability, with a decomposition temperature between 300 and 350 °C, and a high proton conductivity, 60 mS/cm at 70 °C for a polyphenylsulfone with 0.9 sulfonic acid group per repeating unit measured at 100% relative humidity. Moreover, some of the membranes endured immersion in water at temperatures ranging from 20 to 150 °C without swelling extensively, and therefore kept their mechanical stability under these conditions. It was also shown that these membranes retained a high conductivity up to 150 °C under humidifying conditions. The combination of properties make these membranes potential candidates for fuel cells operating at temperatures above 100 °C.     

Interphase formation in model composites studied by micro-thermal analysis

Micro-thermal analysis was used for studying interphases formed in particle-filled composites based on an epoxy resin matrix. The subsurface distribution of the particles can be observed in the conductivity images, while spatial variations in thermal properties can be determined by local thermal analyses.For an anhydride-cured epoxy system filled with porous silica particles, an interphase is observed around the particles. In the ca. 60 μm wide interphase, the glass transition temperature gradually decreases from the bulk value to a value about 10 °C lower. The less densely cross-linked interphase can be detected in the thermal conductivity images and in the local thermal analyses. The interphase formation is attributed to the effect of adsorbed water on the polymerisation mechanism.     

Thermo-physical and impact properties of epoxy nanocomposites reinforced by single-wall carbon nanotubes

The thermo-physical properties and the impact strength of diglycidyl ether of bisphenol F (DGEBF) epoxy nanocomposites reinforced with fluorinated single-wall carbon nanotubes (FSWCNT) are reported. A sonication technique was used to disperse FSWCNT in the glassy epoxy network resulting in nanocomposites having large improvement in modulus with extremely small amount of FSWCNT. The glass transition temperature decreased approximately 30 °C with an addition of 0.2 wt% (0.14 vol%) FSWCNT, without adjusting the amount of the anhydride curing agent. This was because of non-stoichiometry of the epoxy matrix that was caused by the fluorine on the single-wall carbon nanotubes. The correct amount of the anhydride curing agent needed to achieve stoichiometry was experimentally examined by dynamic mechanical analysis (DMA). The storage modulus of the epoxy at room temperature (which is below the glass transition temperature of the nanocomposites) increased up to 0.63 GPa with the addition of only 0.30 wt% (0.21 vol%) of FSWCNT, representing an up to 20% improvement compared with the neat epoxy. The Izod impact strength slightly decreased when the amount of FSWCNT was increased to 0.3 wt%. The excellent improvement in the storage modulus was achieved without sacrificing impact strength.     

Fracture behaviour of polypropylene films at different temperatures: fractography and deformation mechanisms studied by SEM

The fracture surfaces and the deformation micro-mechanisms of one polypropylene homopolymer and three ethylene-propylene block copolymers (EPBC) have been studied by scanning electron microscopy. The results are compared to the essential work of fracture parameters obtained in a previous study with deeply double-edge-notched-tension samples of films fractured between −40 and 70 °C. The homopolymer shows shear-yielding at T≥−20 °C, but at lower T, crazing prevails. The EPBC display shear-yielding for T>0 °C, while a combination of cavitation and shear-yielding occurs at lower T, which is responsible for stress-whitening. The variations of the specific essential fracture work and specific plastic work with T and with ethylene content have been successfully explained in terms of the prevalent deformation mechanisms.     

Investigation of accelerated aging behaviour of high performance industrial coatings by dynamic mechanical analysis

Dynamic mechanical analysis (DMA) represents one of the most important methods for understanding mechanical behaviour of surface coatings providing a valuable link between chemistry, morphology, and performance properties. In this work, dynamic mechanical properties of several high performance industrial coatings were studied extensively. Four commercially available topcoats namely alkyd modified polyurethane (PU), economy aliphatic PU, high performance aliphatic PU and epoxy modified polysiloxane were selected based on their cure chemistries, volume solids, and overall performance. DMA was used to determine elastic modulus, glass transition temperature (T_g), crosslink density and creep behaviour of these coatings. DMA data were substantiated with mechanical and performance properties. Among the coatings, epoxy modified polysiloxane showed the highest T_g of 65.6 °C as well as crosslink density value of 2.24 × 10⁻³ mol/cc which was attributed to its superior mechanical and performance properties. In addition, topcoats were also subjected to artificial aging process in accelerated cyclic corrosion cabinet and QUV-weatherometer, respectively. The consequent changes in their physico-mechanical properties post exposure were also evaluated using DMA and correlated with other performance properties. After aging, the T_g increased substantially for all the coatings irrespective of their exposure type. For example, T_g of economy aliphatic PU increases from 38.4 °C to 52.9 °C and 51 °C after cyclic corrosion and UV-B weathering, respectively. However, crosslink densities either increased or decreased depending on the type of exposure and cure chemistries. These changes were corroborated using the Fourier transform infrared spectroscopy findings. The outcome of this study is expected to generate new insights into the behaviour of these coatings under dynamic mechanical stress and its relation with long term performance properties.     

Adhesive Joint Durability Assessed Using Open-faced Peel Specimens

This paper presents an investigation of the durability of two aluminum-epoxy adhesive systems by means of open-faced peel specimens. A peel analysis model was used to determine the fracture energy from the peel data. Both wet and dry peel tests were conducted in order to distinguish between the reversible and the permanent effects of water. The effects of water on the cohesive properties of the adhesives were also assessed by tension tests. It was found that, for the two-part epoxy adhesive, which plasticized to a large extent, the peel testing should be carried out in a dry state to assess the interfacial weakening. It was also observed that the two-part adhesive was much stiffer in the dry, degraded state, and it was important to take account of such permanent changes in the cohesive properties associated with water uptake when determining the fracture energy from the peel data. In contrast, the one-part epoxy system did not suffer from appreciable cohesive changes, either reversible or permanent. In this case, both wet and dry failure loci were interfacial, and some of the interfacial damage was found to be reversible. Finally, surface analyses of the peel failure surfaces were carried out, and the formation of micro-debonds was identified as a possible mechanism of degradation for the two-part system.